KR20050030458A - Process for self-dispersible coloring agent using lewis acids and ink composition comprising the coloring agent - Google Patents

Abstract

Provided are a method for preparing a self-dispersive colorant by a single step, and an ink composition, a paint and a toner composition containing the self-dispersive colorant prepared by the method which is excellent in long period storage stability and dispersion stability. The method comprises the step of reacting a hydrophilic group-containing halide represented by X-L-R1 and a colorant in the presence of a Lewis acid catalyst to prepare a self-dispersive colorant where a hydrophilic group is introduced represented by (colorant)-L-R1, wherein L is a single bond or -C(=O)-; R1 is a hydrophilic group-containing substituted or unsubstituted C1-C20 alkyl group, a hydrophilic group-containing substituted or unsubstituted C6-C20 aryl group, a hydrophilic group-containing substituted or unsubstituted C2-C20 heteroaryl group, or a hydrophilic group-containing substituted or unsubstituted C7-C20 arylalkyl group; and X is F, Br, I or Cl.

Description

Process for self-dispersible coloring agent using Lewis acids and ink composition comprising the coloring agent}

The present invention relates to a method for preparing a colorant capable of self-dispersion, and an ink composition comprising the same, and more particularly, by introducing a hydrophilic group into the colorant by reacting a colorant with a hydrophilic group-containing halide in the presence of a Lewis acid serving as a catalyst. And a method for producing a self-dispersing colorant.

In general, materials which exhibit an intrinsic color by selectively absorbing or reflecting visible light are called colorants, and such colorants are classified into dyes and pigments.

The dye dissolved in the solvent is a colorant which is fastened to the dyestuffs such as fibers, leather, furs, papers, etc. in a certain way and has fastness to daylight, washing or rubbing, etc., and the pigments insoluble in the solvent are fine particles containing the colorant and are the surface of the dyestuff. It refers to a color which is attached directly to the surface of the chloride by physical methods (for example, adhesion) rather than dyed directly to it.

Dispersion of the pigment containing the colorant in the solvent should be basically carried out in the production of the pigment-type ink, in which the size of the pigment particles, the distribution of the pigment particle size, and the dispersion stability of the pigment particles are effective for pigment dispersion. It is an important factor influencing. In addition, for long-term use of the pigmented ink, aggregation or precipitation of the pigment particles occurs even when the pigment particles dispersed through such a pigment dispersion step are stored for a long time or exposed to changes in the surrounding environmental elements such as temperature changes. Should not.

Most pigmented black inks use carbon black as a colorant, an example of how to disperse carbon black using a dispersant to disperse the carbon black in an ink solvent, as known from US Pat. No. 3,687,887. -Dispersion methods using maleic anhydride copolymers or dispersion methods using hydrophobic polymer dispersants comprising hydrophilic groups such as carboxylic acids, sulfonic acids, sulfates, as known from US Pat. No. 4,697,794. On the other hand, examples of using a random copolymer containing a hydrophilic group by introducing a carboxylic acid as a dispersant include US Pat. US Pat. Nos. 5,085,698 and 5,221,334 also disclose AB type block copolymers or BAB type copolymers in which hydrophilic monomers and hydrophobic monomers are used (for example, hydrophilic monomers are represented by A and hydrophobic monomers are represented by B). Is used as a dispersant, US Pat. No. 5,589,522 uses graft polymers, and US Pat. Nos. 4,959,661 and 5,125,968 use emulsifiers as is known.

When dispersing agents are used to disperse carbon black, conventional dispersants may be used, so that the dispersant may be relatively easy to obtain. However, when dispersing carbon black pigments in water-soluble media, the dispersing agent may be used. It can only be physically adsorbed on the surface of the carbon black, so that an amount of pigment dispersion effect can be obtained only by using an excess dispersant. Therefore, since the amount of water-soluble dispersant must be used in excess of the amount of the pigment to be dispersed, the overall dispersion efficiency is lowered, and since the dispersant is not effectively and stably combined with the pigment, the dispersion stability is poor. In preparing the ink, long-term storage stability is reduced, so that aggregation or precipitation of insoluble particles in the ink is likely to occur. On the other hand, when the block copolymer and the graft copolymer are used as a dispersant, there is a problem in that a high cost is required for the preparation of these dispersants, and when using a general emulsifier, there is a problem that excessive foaming may occur during the dispersing process.

In order to solve the problems caused by the use of dispersants and emulsifiers as described above, a method of dispersing carbon black by surface modification has been devised. US Pat. Nos. 5,630,868 and 5,672,198 disclose methods for transforming carbon black pigments into self-dispersible pigments by reacting carbon black pigments with diazonium salts to introduce hydrophilic groups to the carbon black surface. have.

However, according to the method known in the patent, an aromatic amine compound having a hydrophilic group must be included at the terminal of the compound containing a hydrophilic group and reacting with the pigment to serve to transport the hydrophilic group to the pigment. Silver is difficult to obtain commercially, and since the aromatic amine compound must be converted into a diazonium salt once and then reacted with carbon black, a plurality of reaction processes are required instead of a single process, thereby increasing the complexity and cost of the process. There is a disadvantage.

The technical problem to be solved by the present invention is to solve the above problems, it is easy to disperse in an aqueous liquid medium without the use of a separate dispersant, excellent storage stability and dispersion stability and characteristics of preferred colorants such as color implementation ability, durability, light resistance, etc. At the same time to provide an improved self-dispersing colorant and an ink composition comprising the same.

In order to achieve the above technical problem, the first aspect of the present invention,

In the presence of a Lewis acid catalyst, a hydrophilic group-containing halide represented by Formula 1 is reacted with a colorant to provide a method for preparing a self-dispersing colorant represented by Formula 2 wherein a hydrophilic group is introduced into the colorant.

<Formula 1>

XLR ¹

<Formula 2>

(Colorant) -LR ¹

In the above formula,

L represents a single bond or -C (= 0)-;

R ¹ is a substituted or unsubstituted C ₁ -C ₂₀ alkyl group having a hydrophilic group, a substituted or unsubstituted C ₆ -C ₂₀ aryl group having a hydrophilic group, a substituted or unsubstituted C ₂ -C ₂₀ heteroaryl group having a hydrophilic group Or a substituted or unsubstituted C ₇ -C ₂₀ arylalkyl group having a hydrophilic group;

X is -F, -Br, -I or -Cl.

The hydrophilic group is -OA, -COOA, -SO ₂ A, -SO ₂ NH ₂ , -SO ₂ NHCOT ¹ , -T ² SO ₂ A, -SO ₃ A, -PO ₃ NH ₂ , -PO ₃ A ₂ , -NH ₂ or -N (T ¹ ) ₂ , wherein A is hydrogen, an alkali metal, or Q ¹ , Q ² , Q ³ or Q ⁴ are each independently hydrogen, a C ₁ -C ₂₀ alkyl group or C _6- -NQ ¹ Q ² Q ³ Q ^{4 which} is a C ₂₀ aryl group; T ¹ is a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group or a C ₂ -C ₂₀ heteroaryl group; T ² is preferably a C ₁ -C ₂₀ alkylene group, a C ₆ -C ₂₀ arylene group or a C ₂ -C ₂₀ heteroarylene group.

In order to solve the above another technical problem, the 2nd aspect of this invention provides the ink composition containing the self-dispersion type coloring agent manufactured by the said method.

According to the method of the present invention as described above it is possible to obtain a self-dispersing colorant easily and conveniently through a single step reaction. In addition, the self-dispersing colorant prepared by the above method is easily dispersed in an aqueous medium without using a separate dispersant, and exhibits excellent storage stability and dispersion stability as well as improved color rendering ability, durability, light resistance, and the like.

Hereinafter, the present invention will be described in more detail.

According to the first aspect of the present invention,

In the presence of a Lewis acid catalyst, a method of preparing a self-dispersing colorant represented by the following formula (2) in which a hydrophilic group is introduced into the colorant is reacted with a hydrophilic group-containing halide represented by the following formula (1):

<Formula 1>

XLR ¹

<Formula 2>

(Colorant) -LR ¹

In the above formula,

L represents a single bond or -C (= 0)-;

R ¹ is a substituted or unsubstituted C ₁ -C ₂₀ alkyl group having a hydrophilic group, a substituted or unsubstituted C ₆ -C ₂₀ aryl group having a hydrophilic group, a substituted or unsubstituted C ₂ -C ₂₀ heteroaryl group having a hydrophilic group Or a substituted or unsubstituted C ₇ -C ₂₀ arylalkyl group having a hydrophilic group;

X is -F, -Br, -I or -Cl.

The colorant of Formula 2 thus prepared is a self-dispersing colorant in the form of a hydrophilic group introduced on its surface.

The hydrophilic group electrostatically acts with the aqueous medium after introduction of the pigment so that the pigment containing it can be easily dispersed in the aqueous medium without a separate dispersant. Specific examples of such hydrophilic groups include -OA, -COOA, -SO ₂ A, -SO ₂ NH ₂ , -SO ₂ NHCOT ¹ , -T ² SO ₂ A, -SO ₃ A, -PO ₃ NH ₂ , -PO ₃ A ₂ , -NH ₂ or -N (T ¹ ) ₂ and the like.

Among these, A is hydrogen, an alkali metal, or -NQ ¹ Q ² Q ³ Q wherein Q ¹ , Q ² , Q ³ or Q ⁴ are each independently hydrogen, a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group Preferably ⁴ , T ¹ is a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group or a C ₂ -C ₂₀ heteroaryl group, and T ² is a C ₁ -C ₂₀ alkylene group, C _6- It is preferably a C ₂₀ arylene group or a C ₂ -C ₂₀ heteroarylene group, but is not limited thereto so long as it does not adversely affect the self-dispersion performance of the self-dispersing colorant of the present invention. The hydrophilic group is -OH, -COOH, -SO ₂ H, -SO ₂ NH ₂ , -SO ₂ NHCOCH ₃ ,-(CH ₂ ) SO ₂ H, -SO ₃ H, -PO ₃ NH ₂ , -PO ₃ H More preferred is ₂ , -NH ₂ or -N (CH ₃ ) ₂ .

R ¹ is preferably a C ₁ -C ₁₂ alkyl group; Or a C ₁ -C ₁₂ alkyl group containing a phenyl group or a naphthyl group at the terminal; Or a phenyl group or a naphthyl group. The R ¹ may have one or more hydrophilic groups as described above as long as it does not affect the self-dispersing performance of the self-dispersing pigment.

The colorant is a colorant capable of reacting with a hydrophilic group-containing halide in the presence of a Lewis acid catalyst, and a colorant including a C ₆ -C ₁₅ aryl group or a C ₂ -C ₁₅ heteroaryl group is preferable, and a benzene, naphthalene, pyridine, furan More preferred are colorants comprising a ring of thiophene or pyrrole.

Specific examples of such colorants include carbon black, graphite, vitreous carbon, activated charcoal, activated carbon, anthraquinone, phthalocyanine blue, phthalocyanine green, Diazos, monooazos, pyranthrones, phenylene, quinacridone, indigoid pigments, etc., but are not limited thereto. .

Specific examples of the unsubstituted C ₁ -C ₂₀ alkyl group in Chemical Formulas 1 and 2 of the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like. At least one hydrogen atom is a halogen atom, hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, or C ₁ -C ₂₀ Alkyl group, alkenyl group, alkynyl group, C ₁ -C ₂₀ heteroalkyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ arylalkyl group, C ₆ -C ₂₀ heteroaryl group, or C ₆ -C It may be substituted with ₂₀ heteroarylalkyl groups.

The aryl groups of the formulas (1) and (2) of the present invention may be used alone or in combination to mean a carbocycle aromatic system having 6 to 20 carbon atoms containing one or more rings, which rings may be attached or fused together in a pendant manner. have. The term aryl includes aromatic radicals such as phenyl, naphthyl, tetrahydronaphthyl. The aryl group may have substituents such as haloalkylene, nitro, cyano, alkoxy and lower alkylamino. At least one hydrogen atom in the arylene group may be substituted with the same substituent as in the alkyl group described above.

Heteroaryl groups of the general formula (1) and (2) of the present invention contain 1, 2 or 3 heteroatoms selected from N, O, P or S, and the remaining ring atoms are C 1 to monovalent monocyclic monocyclic or By bicyclic aromatic divalent organic compound is meant. At least one hydrogen atom of the hetero atoms may be substituted with the same substituent as in the alkyl group described above.

The arylalkyl group of the general formulas (1) and (2) of the present invention refers to a substituent having an aryl group or a heteroaryl group as described above at the end of the alkyl group having 2 to 14 carbon atoms. At this time, one or more hydrogen atoms of the alkyl group, the aryl group or the heteroaryl group can be substituted with the same substituent as in the case of the above-described alkyl group.

Of the hydrophilic group-containing halides of the present invention, halides represented by the following general formula (3) are particularly preferable, and the halides have been found to be particularly effective in preparing self-dispersing carbon black pigments.

<Formula 3>

Another preferred halide among the hydrophilic group-containing halides of the present invention is represented by the following formula (4), which has also been found to be particularly effective in preparing self-dispersing carbon black pigments.

<Formula 4>

Lewis acid used in the preparation of the self-dispersing colorant of the present invention is a compound capable of covalently bonding by sharing a non-covalent electron pair with an atom having a non-covalent electron pair, and non-limiting examples thereof include AlCl ₃ , FeCl ₃ , FeBr _3, SnCl ₄ , SbCl ₅ , ZnCl ₂ , BF ₃ , TiCl ₄ and the like. The amount of Lewis acid used will vary depending on the colorant used and the type of hydrophilic group-containing halide, but 0.01 to 5 moles per mole of hydrophilic group-containing halide as described above is suitable. This is because when the Lewis acid is used at less than 0.01 mole, it may be difficult to proceed with the reaction, and when it is used at 5 moles or more, it may be difficult to remove the unreacted Lewis acid and increase the production cost. The temperature for producing the self-dispersing colorant of the present invention will vary depending on the type of the colorant and the hydrophilic group-containing halide used and the reaction solvent, but is preferably from 60 ° C to 200 ° C. Since the reaction for producing the self-dispersing colorant of the present invention proceeds under the distillation condition of the solvent, it is dependent on the boiling point of each solvent used. Since the self-dispersing colorant prepared according to the first aspect of the present invention is introduced with a hydrophilic group through a simple single step process as described above, such a self-dispersing colorant may be selected from fibers, leather, fur, paper, food, pharmaceuticals, Cosmetic, inkjet ink, printing ink, paint, plastic coloring, rubber coloring, furniture manufacturing, printing, papermaking, cosmetic manufacturing, ceramics, etc. can be used in various ways.

According to a second aspect of the present invention, there is provided an ink composition comprising the self-dispersing colorant of the present invention prepared as described above.

The ink composition of the present invention uses an aqueous liquid medium as a solvent, wherein the aqueous liquid medium uses water alone or mixes one or more organic solvents with water to adjust the viscosity and surface tension of the ink composition to an appropriate range. Can be used. The content of such an aqueous liquid medium is 500 parts by weight to 5000 parts by weight, more preferably 1000 parts by weight to 3000 parts by weight based on 100 parts by weight of the self-dispersing colorant. When the content of the aqueous liquid medium is less than 500 parts by weight, it is difficult to disperse the colorant, so that aggregation may occur, and when the amount is more than 5000 parts by weight, the amount of the colorant is too small to implement a desired color. This can happen. The content of the organic solvent can be commonly determined by those skilled in the art so that the self-dispersing colorant of the present invention can be effectively dispersed in an aqueous liquid medium, but it is 10 parts to 1000 parts by weight based on 100 parts by weight of the self-dispersing colorant. desirable. Non-limiting examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol and isobutyl alcohol; Ketones such as acetone, methyl ethyl ketone and diacetone alcohol; Esters such as ethyl acetate and ethyl lactate; Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,2,4-butanetriol, 1,5-pentanediol, 1,2-hexanediol, 1, Polyhydric alcohols such as 6-hexanediol, 1,2,6-hexanetriol, hexylene glycol, glycerol, glycerol ethoxylate and trimethylolpropane ethoxylate; Lower alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether; Nitrogen-containing compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone and caprolactam; A hydrocarbon solvent selected from the group consisting of dimethyl sulfoxide, tetramethylenesulfone and thioglycol is used.

The ink composition of the present invention may further include an additive such as a surfactant, a viscosity modifier, a metal oxide, or an acid or a base.

Surfactants that can be included in the composition of the present invention serves to stabilize the jetting performance in the nozzle by adjusting the surface tension of the composition. Anionic surfactants or nonionic surfactants are used as the surfactant for performing this function.

A nonionic surfactant means a surfactant which is not ionized and dissolved in water, and an anionic surfactant means a surfactant in which an anion portion ionized in water generally exhibits surfactant activity. Specific examples of the nonionic surfactant include hydrophobic units such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkyl phenol ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, and the like. High molecular weight active agents synthesized by block polymerization or graft polymerization with hydrophilic units, and the like.

The content of the surfactant is used as a conventional level based on 0.1 to 5.0 parts by weight based on 100 parts by weight of the ink composition.

The viscosity modifier may be one selected from polyvinyl alcohol, casein, and carboxymethyl cellulose as a material for adjusting the viscosity of the composition to maintain a smooth jetting. Here, the content of the viscosity modifier can be easily determined by those skilled in the art according to the properties of the composition of the present invention, but preferably 0.1 to 5.0 parts by weight based on 100 parts by weight of the ink composition.

The ink composition of the present invention may further comprise an acid or a base. This acid or base serves to stabilize the pigment with respect to the solvent, the content of which is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the composition.

The method for producing an ink composition having the composition as described above is as follows.

First, a self-dispersing colorant, a surfactant, a viscosity modifier, and the like are added to the aqueous liquid medium and mixed, and then the mixture is sufficiently stirred with a stirrer to make a uniform state. Thereafter, the resultant is passed through a filter and filtered to obtain an ink composition according to the present invention.

On the other hand, the self-dispersing colorant of the present invention is not particularly limited to the colorant, and can be used in addition to the ink composition, toner compositions, various paints, coating liquids and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited only to the following Examples. The present invention reveals that the characteristics are evaluated based on the ink, and the method of the evaluation can be applied to liquid toner, dry toner, paint and / or coating liquid, in addition to ink. Hereinafter, only the ink will be described as a representative of the embodiment of the composition to which the self-dispersing colorant is applied, which means that the practice of the present invention is not limited to the ink.

Example

Synthesis Example 1: Preparation of self-dispersing carbon black pigment using halide of formula 3

<Scheme 1>

(Hereinafter, " C " in the reaction formula represents a carbon black pigment.)

According to Scheme 1, 10.2 g of a carbon black pigment (FW-18, manufactured by Degussa) 11.6 g of a halide of Formula 3, 7.8 g of AlCl ₃ and DMF 100 ml were added thereto in a 250 ml round bottom flask, and reacted under reduced pressure for 6 hours. I was. The organic layer of the reaction mixture was extracted with cyclohexane and concentrated to give 16.5 g of the self-dispersing carbon black pigment of Scheme 1 above.

Synthesis Example 2: Preparation of self-dispersing carbon black pigment using halide of formula 4

<Scheme 2>

According to Scheme 2, 10.3 g of carbon black pigment (Regal 330, manufactured by Cabot) 12.4 g of the halide of Formula 4, 13.8 g of SnCl _4, and 100 ml of DMF were added to a 250 ml round bottom flask and reacted under reduced pressure for 6 hours. . The organic layer of the reaction mixture was extracted with cyclohexane and concentrated to give 17.8 g of the self-dispersing carbon black pigment of Scheme 2.

Synthesis Example 3: Preparation of self-dispersing carbon black pigment using halide of formula 5

<Scheme 3>

According to Scheme 3, 10.4 g of carbon black pigment in a 250 ml round bottom flask (Raven 5250, Columbian) 11.9 g of the halide of Chemical Formula 5, 10.9 g of FeBr _3, and 100 ml of DMF were added thereto, and reacted under reduced pressure for 7 hours. The organic layer of the reaction mixture was extracted with cyclohexane and concentrated to give 18.4 g of the self-dispersing carbon black pigment of Scheme 3.

Synthesis Example 4: Preparation of self-dispersing carbon black pigment using halide of formula 6

<Scheme 4>

According to Scheme 4, 10.0 g of carbon black pigment in a 250 ml round bottom flask (No. 25B, manufactured by Mitsubishi) 10.3 g of the halide of Chemical Formula 6, 9.2 g of ZnCl _2, and 100 ml of DMSO were added thereto, followed by reaction under reduced pressure for 8 hours. The organic layer of the reaction mixture was extracted with toluene and concentrated to give 14.8 g of the self-dispersing carbon black pigment of Scheme 4.

Synthesis Example 5: Preparation of self-dispersing carbon black pigment using halide of formula 7

Scheme 5

According to Scheme 5, 10.3 g of carbon black pigment in a 250 ml round bottom flask (No. 258, manufactured by Mitsubishi) 11.5 g of the halide of Formula 7, 10.4 g of TiCl _4, and 100 ml of DMSO were added thereto and reacted under reduced pressure for 8 hours. The organic layer of the reaction mixture was extracted with toluene and concentrated to give 17.1 g of the self-dispersing carbon black pigment of Scheme 5.

Synthesis Example 6: Preparation of self-dispersing carbon black pigment using halide of formula 8

<Scheme 6>

According to Scheme 6, 10.2 g of carbon black pigment in a 250 ml round bottom flask (Valcan XC-72R, manufactured by Cabot) 12.1 g of the halide of Formula 8, 10.6 g of AlCl _3, and 100 ml of DMF were added thereto, and reacted with distillation under reduced pressure for 7 hours. The organic layer of the reaction mixture was extracted with cyclohexane and concentrated to give 15.2 g of the self-dispersing carbon black pigment of Scheme 6 above.

Synthesis Example 7

Scheme 7

According to Scheme 8, 10.2 g of monoazo dye (CI Disperse Red 1) , 11.8 g of the halide of Formula 3, 7.8 g of AlCl _3, and 100 ml of DMF were added to a 250 ml round bottom flask, and reacted under reduced pressure for 8 hours. I was. The organic layer of the reaction mixture was extracted with cyclohexane and concentrated to give 14.2 g of a self-dispersing pigment of Scheme 7.

Example 1 Preparation of an Ink Composition Comprising Self-dispersing Carbon Black Pigment

The ingredients listed in Table 1 below were placed in a 250 ml beaker and mixed and thoroughly stirred for at least 30 minutes. The mixture was passed through a 0.45 mu m filter to prepare an ink composition.

ingredient Content (g) Self-dispersing Carbon Black Pigment Prepared in Synthesis Example 1 4.0 water 77.0 Diethylene glycol 3.0 Ethylene glycol 8.0 glycerin 8.0

Examples 2-6

An ink composition was prepared in the same manner as in Example 1, except that the self-dispersed carbon black pigments prepared in Synthesis Examples 2 to 6 were used instead of the self-dispersed carbon black pigments used in Example 1. Prepared.

Comparative Examples 1 to 6

An ink composition was prepared in the same manner as in Example 1, except that a conventional carbon black pigment, as shown in Table 2, was used instead of the self-dispersed carbon black pigment used in Example 1.

Comparative example number Used carbon black One Manufactured FW-18, Degussa Co. 2 Manufacture of Regal 330, Cabot Co. 3 Manufactured by Raven 5250, Columbian Co. 4 No. 25B, Mitsubishi Co., Ltd. 5 No. 258, Mitsubishi Co., Ltd. 6 Manufacture of Valcan XC-72R, Cabot Co.

The properties of the ink compositions prepared according to the above Examples and Comparative Examples were evaluated according to the following methods.

Experimental Example 1: Long-term storage stability test

100 ml of the ink composition prepared in Examples 1 to 6 and the ink compositions prepared in Comparative Examples 1 to 6 were each contained in 12 heat resistant glass containers, and the inlet of the glass container was sealed and stored in a thermostat at 60 ° C. It was. This was left for 2 months, and then the precipitation of each of the ink compositions contained in the glass container was investigated, and is shown in Table 2 below.

Example Comparative example number One 2 3 4 5 6 One 2 3 4 5 6 evaluation O O O O O O O X O X X O

O: No precipitate was observed.

X: A precipitate was observed.

As can be seen from Table 3, it can be seen that the ink composition according to the present invention does not produce a precipitate even when left for two months. In particular, in the ink compositions prepared in Comparative Examples 2, 4 and 5, whereas precipitates are observed, the self-dispersed carbon of the present invention incorporating hydrophilic groups into the conventional carbon black pigments used in Comparative Examples 2, 4 and 5 above. No precipitates were observed in the ink compositions of Examples 2, 4, and 5 using the black pigment. From this, it can be seen that the self-dispersing pigments prepared according to the present invention exhibit very long-term storage stability compared to conventional pigments. .

Experimental Example 2: Dispersion Stability Test

The time taken when the ink composition prepared in Examples 1 to 6 and the ink compositions prepared for Comparative Examples 1 to 6 were subjected to pressure filtration in a 1 μm porous membrane were measured, respectively. Thereafter, each of the ink compositions prepared in Examples 1 to 6 and 50 ml of the ink composition prepared in Comparative Example 1 were each placed in a 100 ml PP bottle, and the PP bottle was left for 4 hours at 60 ° C. and 4 hours at −40 ° C. The process was repeated 10 times (hereinafter referred to as "TC (Thermal Cycle)") and then filtered under pressure in a porous membrane of 1㎛, the time taken for the pressure filtration was measured. The time measured before TC and the time measured after TC were substituted into Equation 1 below to evaluate the dispersion stability parameter A of each composition, and are shown in Table 3 below.

[Equation 1]

A = [filtration time (after TC) -filtration time (before TC)] / filtration time (before TC) X 100 (%)

Example Comparative example number One 2 3 4 5 6 One 2 3 4 5 6 evaluation O O O O O O O △ X O △ △

O: A <10 (excellent dispersion stability)

△: 10 <A <20 (medium dispersion stability)

X: A> 20 (poor dispersion stability)

As can be seen from Table 4, the ink composition according to the present invention is dispersed without precipitation or aggregation after TC, and it can be seen that it has excellent dispersion stability. In particular, A of the ink compositions prepared in Comparative Examples 2, 5 and 6 was 10 to 20, in particular A of the ink composition prepared in Comparative Example 3 exceeded 20, but in Comparative Examples 2, 3, 5 and 6 A of the ink compositions of Examples 2, 3, 5 and 6 using the self-dispersing carbon black pigment of the present invention incorporating hydrophilic groups into the conventional carbon black pigments used was less than 10, from which it was prepared according to the present invention. It can be seen that the self-dispersed pigments exhibited significantly improved dispersion stability compared to the conventional pigments.

Experimental Example 3: Nozzle Clogging Test

Each of the ink compositions prepared in Examples 1 to 6 and the ink compositions prepared in Comparative Examples 1 to 6 were placed in an ink cartridge M-50 (manufactured by Samsung), which was then used for two weeks at room temperature (25 ° C) and low temperature (-18 ° C). After leaving it for a while, the printer (MJC-2400C, manufactured by Samsung) was printed on plain paper (Premium Copy paper, manufactured by Samsung), and the nozzle was clogged to evaluate the extent to which ink cannot be discharged. 5 is shown.

Example Comparative example number One 2 3 4 5 6 One 2 3 4 5 6 Evaluation (room temperature) O O O O O O △ X O △ O O Evaluation (low temperature) O O O O O O X X O X O O

O: No clogging of all nozzles is observed

Δ: 1 to 2 nozzle clogs are observed

X: 3 or more nozzle clogs observed

As can be seen from Table 5, it can be seen that the ink composition according to the present invention can be used without nozzle clogging even after being stored at room temperature or low temperature. In particular, when using the ink compositions prepared in Comparative Examples 1, 2 and 4, clogging of one or two nozzles or three or more nozzles occurred, whereas the conventional carbon blacks used in Comparative Examples 1, 2 and 4 were observed. No ink clogging was observed in the ink compositions of Examples 1, 2, and 4 using the self-dispersing carbon black pigment of the present invention incorporating a hydrophilic group into the pigment. It can be seen that has a significantly improved long-term storage stability and dispersion stability compared to the conventional pigments.

Since the self-dispersing colorant of the present invention can be prepared by a method in which the hydrophilic group is easily introduced into the colorant through a single step process, the cost required for the manufacturing process of the self-dispersing colorant of the present invention can be greatly reduced. In addition, the ink composition using the self-dispersing colorant of the present invention is excellent long-term storage and dispersion, such as no aggregation or precipitation after long-term storage or temperature change without impairing the basic properties of the pigment such as durability, color implementability, light resistance, etc. Stability.

Such self-dispersing colorants of the present invention, as well as the ink composition, fibers, leather, fur, paper, food, pharmaceuticals, cosmetics, paint, printing ink, inkjet ink, plastic coloring, rubber coloring, furniture manufacturing, printing, papermaking, As a variety of pigments for cosmetic production, ceramics, etc., it is possible to drastically improve the colorant dispersion step that should be basically performed in the industrial field.

Claims (16)

In the presence of a Lewis acid catalyst, a hydrophilic group-containing halide represented by Formula 1 is reacted with a colorant to prepare a self-dispersing colorant represented by Formula 2 wherein a hydrophilic group is introduced into the colorant. <Formula 1> XLR ¹ <Formula 2> (Colorant) -LR ¹ In the above formula, L represents a single bond or -C (= 0)-; R ¹ is a substituted or unsubstituted C ₁ -C ₂₀ alkyl group having a hydrophilic group, a substituted or unsubstituted C ₆ -C ₂₀ aryl group having a hydrophilic group, a substituted or unsubstituted C ₂ -C ₂₀ heteroaryl group having a hydrophilic group Or a substituted or unsubstituted C ₇ -C ₂₀ arylalkyl group having a hydrophilic group; X is -F, -Br, -I or -Cl. The method according to claim 1, wherein the hydrophilic group is -OA, -COOA, -SO ₂ A, -SO ₂ NH ₂ , -SO ₂ NHCOT ¹ , -T ² SO ₂ A, -SO ₃ A, -PO ₃ NH ₂ , -PO ₃ A ₂ , -NH ₂ or -N (T ¹ ) ₂ , wherein A is hydrogen, an alkali metal, or Q ¹ , Q ² , Q ³ or Q ⁴ are each independently hydrogen, C ₁ -C -NQ ¹ Q ² Q ³ Q ^{4 which} is a ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; T ¹ is a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group or a C ₂ -C ₂₀ heteroaryl group; T ² is a C ₁ -C ₂₀ alkylene group, a C ₆ -C ₂₀ arylene group or a C ₂ -C ₂₀ heteroarylene group. The method according to claim 2, wherein the hydrophilic group is -OH, -COOH, -SO ₂ H, -SO ₂ NH ₂ , -SO ₂ NHCOCH ₃ ,-(CH ₂ ) SO ₂ H, -SO ₃ H, -PO ₃ NH ₂ , -PO ₃ H ₂ , -NH ₂ or -N (CH ₃ ) _{2 The} method for producing a self-dispersing colorant, characterized in that. The compound of claim 1, wherein R ¹ is a C ₁ -C ₁₂ alkyl group; Or a C ₁ -C ₁₂ alkyl group containing a phenyl group or a naphthyl group at the terminal; Or a phenyl group or a naphthyl group. The method for producing a self-dispersing colorant according to claim 1, wherein the colorant comprises a C ₆ -C ₁₅ aryl group or a C ₂ -C ₁₅ heteroaryl group. The method for producing a self-dispersing colorant according to claim 4, wherein the colorant comprises a ring of benzene, naphthalene, pyridine, furan, thiophene or pyrrole. The method for producing a self-dispersing colorant according to claim 1, wherein the hydrophilic-containing halide is represented by the following general formula (3). <Formula 3> The method according to claim 1, wherein the hydrophilic-containing halide is represented by the following formula (4). <Formula 4> The method of claim 1, wherein the Lewis acid catalyst is AlCl ₃ , FeCl ₃ , FeBr _3, SnCl ₄ , SbCl ₅ , ZnCl ₂ , BF ₃ , TiCl ₄ . The method for producing a self-dispersing colorant according to claim 1, wherein the Lewis acid catalyst is used at 0.01 to 5 moles per mole of the hydrophilic group-containing halide. The temperature of claim 1, wherein the temperature is 60 to 200 ℃ Method for producing a self-dispersing colorant, characterized in that carried out under. An ink composition comprising a self-dispersing colorant prepared by the method of any one of claims 1 to 11. 13. The method according to claim 12, comprising water or a mixture comprising water and at least one organic solvent as an aqueous medium, wherein the aqueous medium is used in an amount of 500 parts by weight to 5000 parts by weight based on 100 parts by weight of the self-dispersing colorant. An ink composition. 13. The ink composition of claim 12, further comprising a surfactant, a viscosity modifier, an acid or a base. A paint comprising a self-dispersing colorant prepared according to any one of claims 1 to 11. A toner composition comprising a self-dispersing colorant prepared according to any one of claims 1 to 11.